Halogen-2-hydroxy-4-butenes-2 and their derivatives and methods of producing same



Patented Mar. 5, 1940 PATENT OFFICE HALO GEN-Z-HYDROXY- l-BUTENES-Z AND THEIR DERIVATIVES AND METHODS OF PRODUCING SAME Arnold M. Collins, Wilmington, net, assignor to E. I. du Pont de Nemours & Company, Wil mington, Del., a corporation of Delaware No Drawing. Application August 14, 1936,

Serial No. 96,049

This invention relates to organic hydroxyl compounds and their esters and to a process for producing the same. More particularly, it relates to halogen containing unsaturated organic hydroxyl compounds and their esters.

It is an object of this invention to prepare halogen-2-hydroxy-4-butenes-2 and their esters, such compounds having the comprehensive formula CH3-C(X)=CH-CH2OR, where X is halogen and R is hydrogen or an oxygen-containing acid radical. A further object is to prepare homologues of the halogen-2-hydroxy-4-butenes- 2 and their esters. A more specific object is to prepare chloro-2-hydroxy-4-butene-2 and its 5 esters.

2,4-butenes-2 with aqueous alkali. Another object is to substitute a hydro-xyl group on the fourth carbon atom of dihalogen-2,4-butenes-2 for the halogen atom thereon. Still a further 20 object is to esterify halogen-2-hydroxy-4-butenes-2. Other objects will appear hereinafter.

These objects are accomplished by subjecting a dihalogen-2,4-butene-2 or a homologue of a dihalogen-2,4-butene-2 to hydrolyzing conditions 25 such as treatment with steam under pressure orv with aqueous alkaline solutions, e. g., with aqueous solutions of alkali metal hydroxides or of salts thereof with weak acids. By this treatment the halogen. atom on the fourth carbon 80 atom is replaced by a hydroxyl group. The resulting hydroxyl compounds may be isolated and if itis desirable esterified by reaction with an oxygen-containing acid or ester-forming derivative thereofsuch as an acid halide or an an- 35 hydride.

Apreferred modification of the invention involves reacting dichloro-2,4-butene-2 with aqueous alkali, particularly, aqueous solutions of salts of sodium or potassium hydroxides with weak 40 acids such as carbonic, whereby chloro-2-hydroxy-4-butene-2 is formed. A further preferred modification of the invention involves esterifying this chloro-Z-hydroxy-4-butene-2 with a carboxylic acid.

45 The following examples are included only for the purpose of illustrating the invention and, therefore, it is to be understood that they are not to be construed as limiting the scope of the in- I vention.

EXAMPLE 1.C'hZoro-2-hydro:cy-4-butene-2 An aqueous solutionof 212 gm. (2 moles) of sodium carbonate in 500' cc. of water was vigorously agitated with 250 g. (2 moles) of di- 56 chloro-2,4-butene-2 at 90 C. for 18 hours.

A further object is to react dihalogen- The 26 Claims. (01160-471) reaction mixture was subjected to ether extraction and the ethereal solution dried with anhydrous potassium carbonate and fractionated. A 53% yield (113 gm.) of chloro-2-hydroxy-4- butene-2 was obtained. This compound had the 5 following properties: B. P. 565 C./9 mm.;

df,1.1l20; N 3, 1.4687 1 Upon analysisit was found to contain 44.92% carbon, 6.79% hydrogen and 33.38% chlorine. in The calculated values for a compound of the formula 041-11001 are 45.05% carbon, 6.57% hydrogen and 33.33% chlorine.

EXAMPLE 2.Dimtro-3,5-benzoate of chloro-Z- hydroxy-4-butene-Z This ester was readily obtained by heating 3,5-dinitrobenzoyl chloride with chloro-2-hy droxy-4-b-utene-2 on a steam bath until fumes of hydrogen chloride ceased to be evolved. The dinitrobenzoate after recrystallization from a mixture of ethanol and water melted at 72-3 0. and was found upon analysis to contain 43.96% carbon and 2.85% hydrogen. The calculated values for a compound of the formula I C11H9O6N2Cl are 43.92% carbon and 2.99% hydrogen.v

Similarly, esters of chloro-2-hydroxy-4-buene-2 with other oxygen-containing acids may be prepared. Examples of such acids are inorganic acids such as sulfuric and organic acids such as sulfonic acids (e. g., benzene sulfonic acid) and carboxylic acids. Esters of the latter type constitute the preferred embodiment of the'invention. Examples of carboxylic acids, esters of which with chloro-2-hydroxy-4-butene2 may-be prepared, are formic, acetic, propionic, butyric, isobutyric, palmitic, oleic, crotonic, abietic, stearic, benzoic, phenylacetic, oxalic, succinic, adipic, phthalic, salioyclic, andp-amino-benzoic acids. 0 The acid may be aliphatic, aromatic, heterocyclic, or alicyclic; saturated or unsaturated; monobasic or polybasic; and it may or may not contain such other groups as alcohol, nitro, amino, halogen, alcoholic hydroxyl, phenolic hydroxyl, and. the like. a

The invention is illustrated in the above specific description by applying it to dichloro-2,4- butene-Z but as has beenstated other dihalogen- 2,4-butenes-2 may be likewise employed. Sim-- ilarly homologues of these dihalogenbutenes such as those corresponding to the formula carbon radical and those corresponding to the 56,

formula CI-I3C(X) =CR CI-I(X') (R') in which X and X are halogen and R and R, are hydrogen or hydrocarbon radicals but are never both hydrogen may be used. The halogen atoms may be chlorine, bromine or iodine and while preferably the same, they may be different. Specific dihalogenbutenes which may be employed 1 in the present invention are dichloro-2,4-buvaried within rather wide limits.

tene-2, dibromo-2A-butene-2, diiodo-ZA-butene 2, chloro-2-bromo-4-butene-2 and bronco-2- chloro-4-butene-2. 1 fa The dihalogenbutenes may be prepared as described in a copending application of Carothers'and Collins, Serial No. 688,030,-filed Septem ber 2, 1933, now matured into U. S. Patent No. 2,102,611. Similarly by the addition of a hydrogen halide to the hydrocarbon substituted monohalogenbutadienes described in Jacobson, U. S. Patent 1,950,440 and Carothers and 001iman, U. S. Patent 1,950,441, it is possible to obtainthe homologues of the dihalogenbutenes described above. In general, homologous dihalogenbutenes are formed in the same manner as the dihalogenbutenes themselves, although homologous, butadienes do not add the hydrogen halide quite so readily. Further discussion of these inventions will bewith particular reference to the dihalogenbuten'es themselves but it is to be understood that the same general considerations are'applicable to the homologous dihalogenbutenes.

The dihalogenbutene may be reacted with solutions of alkali metal hydroxides, such as those of sodium, potassium, caesium and. lithium. Al'- ternatively, it may bereacted with an aqueous solution of alkali metal salt which in aqueous solution gives an alkaline reaction,typical salts ofthis class being sodium, potassium and ammonium carbonates. A third alternative is to react the dihalogenbutenewith steam under pressure. It has been found that the reaction may be conveniently carried out with both reactants dissolved in a common solventv such as dilute alcohol. In any of these cases, the mobile halogen atom (which is v,the one attached to the end carbon atom) displaced with the separation of alkali metal halide or hydrogen'halide and formation of halogen-2-hydroxy-4-butene-2. Dichlorobutene with solid potassium hydroxide gives monovinylacetylene and perhaps chloro-2- butadiene-1,3. I

The reaction time and temperature may be Thus, the reaction will take place at'temperatures between room temperature (about 25 C.) and the boiling point of the mixture, or higher if the reaction is carried out in a closed system. Depending on the other conditions, the reaction time may vary between 3 and 72 hours. Difierent pairs of reactants may require diiferent times and temperatures, or, may have difierent optimum reaction conditions but such changes are a matter of simple test and will. be apparent to those skilled in the art.

In the above example, the full amounts of both reactants used are brought together at once. It is possible, however, to vary this method, for example, by adding the dihalogenbutene dropwise to the aqueous alkali or other bydroxylating means, or vice versa. Preferably, however, the reactants are agitated together. As indicated above, superatmospheric pressures may be employed if desired. Generally, the reactants are brought together in suchproportions that the aqueous alkali or other substance to be reacted with the dihalogenbutene is present in considerable excess over the amount required to react with the dihalogenbutene. About 2 equivalents of alkali salt per equivalent of dihalogenbutene has been found satisfactory Other proportions may be used, however, the amounts of the invention.

The halogen-2-hydroxy-4-butene-2 formed by the process of this invention may be removed. from the reaction mixture in various ways, for example, by extraction of the reaction mixture with ether followed by drying and fractionation of the ethereal solution. After separation of the halogen-2-hydroxy-4=-butene-2, it may be further reacted, .forexample, esterified to yield a wide variety of other compounds. The esters of the halogen 2 hydroxy-4-butenes-2, for example, chloro-2-hydroxy-4-butene-2 may be prepared by any of the known methods, such as by using the acids themselves with or without'catalysts, or by using the anhydrides or chlorides of the acids. The esters may be isolated by any desired means depending on their physical properties. Suitable means for isolating any particular ester will be apparent to those skilled in the art and particularly, in view of the diversity of methods which may be employed, need not be discussed further herein. Q

This invention provides a simple and convenient method for synthesizing halogen -2-hydroxy-4-butenes-2 and their esters, particularly, chloro-2-liydroxy-4-butene-2 and its esters. "The starting dihalogenbutenes are readily'available' derivatives of vinylacetylene. 'These'new compounds would be difiicult to prepare by other methods.

selves readily to various syntheses and their esters are useful as solvents, perfume chemicals and pharmaceuticals.

It is apparent that many widely different emwhich will be readily apparent to those practicing The halogen-2-hydroxy-4-butenes+2, particularly, the chloro, compound, lend them bodiments of this invention may be made without departing from the spirit and scope thereof, and,

therefore, it is not intended to be limited except 5. The process which comprises hydrolyzing a.

dihalogen-ZA-butene-Z to a halogen-2-hydroxy- 4-butene-2.

6. The process which comprises hydrolyzing dichlor o 2,4 -butene-2 to chloro-2-hydroxy-4- butene-2 with steam. i r

7. The process which comprises hydrolyzing a.

dihalogen-2A-butene-2 to a halogen-,2r-hydroxye dichloro-2,4-butene-2 to chloro-2 -hydroxy- 4 -bu-f tene-2 withaqueous alkali and separating the dichloro-2A-butene-2 to chloro-2-hydroxye4-butene-2 from the reaction mixture.

11. The process of claim 7 further characterized in that an excess of alkali is used.

12. The process of claim 8 further characterized in that an excess of alkali is used.

13. The process" which comprises hydrolyzing chloro-2-hydroxy-4- butene-2 with an excess of aqueous alkali at a temperature substantially above room, temperature and separating thechloro-2-hydroxy-2-, butane-2 from the reaction mixture.

14. The process which comprises hydrolyzing dichloro-2,4-butene-2 tochloro-2-hydroxy-4- butene-2 with an aqueous solution of sodium carbonate by vigorously agitating for 18 hours at 90 C., the two reactants being present in substantially the same molecular proportions, subjecting the reaction mixture to an ether extraction, drying the ethereal solution with anhydrous potassium carbonate and separating the chloro-2-hydroxy-4-butene-2 by fractional distillation. Y

15. A compound of the group consisting of compounds of the formula in which X. is a halogen atom, Y is a member of the group consisting of hydroxyl and carboxylic acid ester radicals and R R and R are mem- 17..The process which comprises reacting dichloro-2,4-butene-2 with an aqueous solution of sodium carbonate by agitating them together,

the two reactants being present in substantially the same molecular proportions, treating the reaction mixture with an organic solvent for chloro-2-hydroxy-4-butene-2 to extract the same, drying the extract and separating chloro- 2-hydroxy-4-butene-2 therefrom by distillation.

18. A compound as described in claim 15, further characterized in that R 1'1. and R are v hydrogen.

19. Dinitro-3,5-benzoate of chloro-2-hydroxy- 4-butene-2.

20. The process which comprises .hydrolyzing a dihalogen-ZA-butene-Z to a halogen-2-hydroxy-4-butene-2 and then esterifying the hydroxy compounds with a carboxylic acid.

21. A process as described in claim 16, further characterized in that thehydroxy compound a halogen-2-hydroxy-4-butene-Z-with a carboxylic acid.

25.The process which comprises esterifying chloro-2-hydroxy-4-butene-2 with a carboxylic acid.

26. The process of forming the dinitro-3,5- benzoate of chloro-2-hydroxy-4-butene-2, which comprises reacting chloro-2-hydroxye4-butene- 2 with3,5-dinitrobenzoyl chloride.

ARNOLD M. cornms.

20 formed is then esterified with a carboxylic acid.

CERTIFICATE OF CORRECTION. Patent No. 2,192,299. March 5, l9LLO.

ARNOLD M. COLLINS.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5 first column, line 11, claim 15, for "chloro2hydroXy-2" read chloro-2-hydroxjr- LL; and that the said Letters Patent should be read with this correction therein that the same mayconform to the record of the case in the Patent Office. I

Signed and sealed this 9th day of April, A. D. l9l O.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents. 

